Arylides of naphthalene dicarboxylic acids and process of making same



Patented May 10, 1932 l I Lnoi oLn-Lesm AND. osm HALLEn or oFFENBnomon-THn-MMN, GERMAN QAS- SIGNORS TO-GENERAL ANILINE worms, me, on NEW YORK, my; A CORPORATION p11 DELAWARE.

4 mm or NAPETHALEnE nIcARBoXYLIc ACIDS AND rnocnssfor MAKING at Drawing. Application filed October 23', 192a, Serial No.401,973, and in Germany member-1; 192s.

' our present invention-[relates to new and V valuable condensation products of the naph- .thalene series and to a process of preparing the same, more particularly-it relates to comcorfe'spond to the general formula:

HOary1NHCO-naphtha1eue+ CO NH ;ary1OH wherein one (IO-group is attached to the n phthalene nucleus represented by the following schem a 'Y-position and the other. CO-group in one of the Yi-positions, and wherein each aryl nu cleus may contain further substituents.

These compounds-are obtainable accord-' ing to our process by condensing a naphthalene dicarboxylic acid chloride, in which the carboxylic acid chloride groups are attached in the above signifie'd -positions of the naphthalene nucleus, with a hydroXy-aryl-amine.

Particularly valuable products are- -those in which the one CO-group is attached to the naphthalene nucleus in the 1-po'sition and the other CO-group in theor 5-positi'on. The naphthalene 'dicarboaylic acid chlo-- rides may also be applied in situ. In this "case instead of the chlorides the corresponding carboxylicacids themselves are used with the addition ofa chloride of phosphorus. v The reaction is advantageously carried outin the presence ofa diluent which may be capable-'ofbinding acids; 1 V

In theform oftheir alkali-metal salts the new compounds, though containing neither sulfonic nor carboxyli'c acid groups, are soluble in water in a degree sufficient for technical-purposes and show an a'Ifinity,tothevegetable-fiber which permits, their'useffor impregnating cotton goods; f 1 Inordertd further illustrate ourv invention vthe;following {examples are given, the parts UN 'rEn'sTATE S PATENT-9 OFF C l being by weight and all temperatures in cenv; tigrade degrees; but we wish it to be under-1f; V stood that We are not limited tofthe'particuf lar, p tioned therein. I

oducts nor reaction conditions iiieii I aphthalene 'is-dicarboxy lie" line. Then parts of phosphorus trichlo-wv ride are allowed to run in slowly at 102t'o The mass is heated at forb'hours" and thereafter poured into dilute hydro- Ychloricflacid The precipitate'formedis filtered off and stirred with. a'sodiuln carbonate 1 solution untilit shows an alkaline reactiom Then dimethylaniline isremoved by means of steam and the reaction product is further' f purified by dissolving it in a' causticsodaf solution and again precipitating withk'c'ar-iit -bonicacid.. In i this manner naphthalene l".5-dicar boXylic-di-(3-hydroxy-phenylamide) is obtained. It corresponds to the formula f oo-Nn-Q I OH on V \ i V V ONE-74130 and melt's at 295 -2989. V

In an analogous manner naphthalene-lb d1carboXyl1c-di(4 hydroxyphenylamide) melting at 325330 may be produced by starting from lemme-phenol insteadfofi'lr amino-phenol. L i

Both compounds are insoluble intheusual organic solvents.- v 1 The reaction "takes place in manner, yielding isomeric product'sgrwhenkg 7 starting from" naphthalene; 2.6 orl2'.7-dicar bo'xy'lic-acids. 1 mand 60 parts of phosphorus trichlorideare allowed to react in the manner described in Example 1. Naphthalene-1.5-dicarboxylicdi(2-methyl-5-hydroxy-phenylamide) thus obtained corresponds to the formula:

00-NH-Q W OH Itmelts at 190198 and may also be purifled by dissolving it in a caustic soda solution and precipitating with carbonic acid.

- *A'similar product is obtained by replacing in this example l-methyl-Q-aminol-hydroxy-' The temperature israised to 110 and thus maintained for 8 hours. Thereafter the mass is poured into dilute hydrochloric acid. The precipitate formed is filtered ofl', mixed with an excess of a soda solution and freed from *dimethylaniline possibly still adhering by ,means of-steam. The condensation product is purified as described in the foregoing ex amples. It corresponds to the formula:

and melts at 270273. With the same success pyridine may be used instead of dimethylaniline. v r

' Example 1 8 V r 253 parts of naphthalene1.4-dicarboxylic acld chloride'and 218 parts of 3-amino-phenol are introduced into 500 parts of benzinei The 'mass is heated andke'pt at boiling temperature for 8 hours and then mixed j with an excessof a soda solution. The solvent is distilled ofi by'steam and the reaction product purified in the above mentioned manner; It

is identical to that of Example 3.

I Example-5 .A.mixture of 253 parts ofnaphthalene-lfidicarboxylic acid chloride, 218 parts of 3- aminophenol and 500 parts of acetone is boiled'for 8 hours.- The mass is worked up according to the foregoing examples and yields a product identical to that of Example 1.

, Example 6' I 253 parts ofnaphthalene-lA-dicarboxylio acid chloride and 318 parts of 1-amin0-5- naphthol are introduced into 3000 parts of acetone." The massis heated and kept'at boiling temperature for '8 hours, then poured into water and made alkaline by means *of soda. The formed precipitate is filtered oil and treated at '3040 with dilute hydro-" chloric acid. The residue is purified asdescribed in the foregoing examples. The" condensation product thus obtainedcorresponds to theformula: i

v oo-NH 1 0H 7 00-NH It is soluble in caustic alkali solutions, insoluble in soda solution and in organic solvents.

Ewample 7 Amixture of 253 parts naphthalene 1.5-dicarboxyiic acidchloride,' 318 parts of Lamino-7-naphthol and 3000 parts of acetone is treated according to Example 6. The product thus obtained corresponds to the formula: 8

It shows similar properties to that of Example 6. 1

The "condensation of naphthalene 1.5-dicarboxylic acid chloride=with 1 amino-5- naphthol yields a similarproduct.

' Exa les parts of naphthalenelll-discharboxylic acid chloride and 318 parts offl-amino-7- naphthol are introduced into 2500 parts of dimethylaniline. The temperature is gradually raised to 80. 90 and thus maintained Then the mass is poured into for 8 hours. dilute hydrochloric acid.- The precipitate'is filtered ofl, mixed with an excessof a soda s0- y lution and freed from dimethylaniline by steam distillation. The condensation prod? uct may be further purified by dissolving it in a'caustic soda solution and precipitating withcarbonicacid It corresponds'to the 015 mula:

.CO-NH It exhibits similar properties as the products of the foregoing examples. 1

WVe claim: I g

1. A process which comprises treating a naphthalene dicarboxylic acid chloride of i the formula in which one CO-group is attached to the naphthalene nucleus represented by the following scheme 1 in the X-position and the other CO-group in one of the X -positions, or one CO-group is attached to the naphthalene nucleus in the Y-posit-ion andthe other CO-group in one of the Y -positions, with a hydroXy-am'ino compound of the general 7 formula HQT-R-OH whereinR stands for a benzene, toluene or naphthalene radicle, in the presence of a diluent.

1 2. vA.process,which comprises treating a naphthalene dica-rbcxylic acid chloride of in the .X-position and other'CO-group in one of the X -positiongor one CO-group is attached to. the naphthalene nucleus in the Y-position and the other CO-group in one of the Y -p ositions, with a hydroXy-amino compound-of the general formula H NR-'OH all which the ."one- C0" wherein R standsiofr abenzene itoluene or naphthalene :radicle; in the presence of 7 a diluent "capableof binding acids.

3.- A process which comprises-treatinga naphthalene dicarboxylic acid chloride of the; formula- 1- 30001" V i 3 in which theone .OOGl-group isiattached to the naphthalene nucleus in thelposition and the other CO-group; in the 4- or 5-position,- with a hydroXy-amino compoundfof the general fOrmula H N-ROH wherein R stands for a benzene, toluene or naphthalene radicle, inthe presence of a diluent capable of binding acids.

4. A process which comprises treating a.

' naphthalene dicarboxylic acid of the formula hthl I nap ae1 1e Q v H-group to the naphthalene nucleus in the l-position and the other COOI-Lgroup in the t- '0r 5-l position, with'a chloride of phosphoru's' and a hy'droXy-annno compound of the general formula H' N'R--OH wherein stands for a benzene, toluene or naphthalene radicle in. the presence of an acid-binding agent. I

5. A process which comprises treatinga is attached naphthalene dicarboxylic ac d of the formula V a hthal /OOOH i acoouff i in which the one CO'OH-group is attached to the naphthalene nucleus in the'l-position and trim" the other COOH-group in'the 4:7. 01" 5-posi-' tion,wwith phosphorus trichlonidejandaila:

hydroxy-amino compound of the general 1 05.

formula H NR OH wherein R stands for a benzene, toluene or naphthalene radicle in the presence' of a tertiary organic base. 6. A process which comprises'treating a naphthalene dicarboxylic. acid of the formula . in which the one c0oH.gm.1 is a ias. to V the naphthalene nucleus in the 1-position and x the other COOH-group in the 4 or- 5-position, with phosphorus trichloridefand a hydroXy-phenylamine of i the general for mula:

wherein mans'hydiogenioi the presence of atertiary organic base? 7'. 'A process ,whichcomprises; treating a W naphthalene dicarboxylic acid of the-ion mula v 9 ii 1 1 to the naphthalene nucleus in the 1-position and the other COOK-group in the 4: or position, with phosphorus trichloride and 3- amino-phenol, in the presence of a" tertiary organic base. w

8. As new compounds the condensation products of the naphthalene series corre sponding to the general formula:

wherein one CO-group is attached to the naphthalene nucleus-represented by the following scheme in the X-position and the other CO-group in one of the X -positions, or one (JO-group is attachedv to the naphthalene nucleus in the Y-position and the other GO-group in one of the Y positions, and wherein R stands for a benzene,- toluene or naphthalene radicle, which compounds are soluble in caustic alkalies but insoluble in'sodium carbonate solution and in organic solvents. V

9. Asvnew compounds the condensation products of the naphthalene series corresponding to .the general formula no 7 g p v I on wherein one GO-group is attached to the i naphthalene nucleus represented by the following scheme 40 V sponding to the general formula wherein the one CO-group'is attached to the naphthalene nucleus in the l-position and the other- CO-group inithef l or fi-positio'ng and wherein'the Xs mean hydrogen or methyl groups, which compounds are soluble in caustic alkalies but insoluble in sodium carbon ate solution and in organic solvents.

11. As new compounds the condensation products. of the naphthalene series corresponding to the general formula:

NHO 0naphthalene c warn-O H on wherein the one COgroupi's attached to the naphthalene nucleus in the 1-position and the other CO-group in the 4- or 5-position, which compounds are soluble in caustic alkalies .but insoluble .in'sodium carbonate solution and in organic solvents. V 12. As a new compound thec'ondensation product of the naphthalene series corresponding to the formula:

which compound is soluble in caustic alkalies but insoluble in sodium carbonate solution and in organic solvents.

13. As a new compound the condensation product of the naphthalene series corresponding to the formula: v

"OO NH f V hu OH: ca -i I HO/ if i which compound is soluble 'in caustic alkalies but insoluble in sodium. carbonate-solution and in organic solvents.

14:. As a new compound the condensation product of the naphthalene series corresponding to the formula oo-nn-O I a a which product is soluble in caustic alkalies but insoluble in sodium carbonatesolution and in organic solvents. 1 .In testimony whereof, we affix our signatures. l r

.. LEOPOLD LASKA.

- OSKAR. 

